Collisional Deactivation of CO2(00o1) and N2O(00o1) by Toluene Isotopomers: Near-Resonant Energy Transfer for N2O(00o1)
Date
1997
Authors
Poel, K.
Glavan, C.
Alwahabi, Z.
King, K.
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Journal article
Citation
Journal of Physical Chemistry A, 1997; 101(31):5614-5619
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Abstract
The time-resolved infrared fluorescence (IRF) technique has been used to study the vibrational deactivation of CO<inf>2</inf>(00°1) and N<inf>2</inf>O(00°1) by C<inf>6</inf>D<inf>5</inf>CH<inf>3</inf> and C<inf>6</inf>H<inf>5</inf>CD<inf>3</inf> at ambient temperature (295 ± 2 K). The bimolecular deactivation rate constants were found to be (242 ± 17) × 10<sup>3</sup> and (145 ± 5) × 10<sup>3</sup> Torr<sup>-1</sup> s<sup>-1</sup>, respectively, for the deactivation of CO<inf>2</inf>(00°1), and (253 ± 13) × 10<sup>3</sup> and (376 ± 20) × 10<sup>3</sup> Torr<sup>-1</sup> s<sup>-1</sup>, respectively, for the deactivation of N<inf>2</inf>O(00°1). Experimental deactivation probabilities are calculated and compared with our previous data for deactivation of the same two excited molecules by the colliders C<inf>6</inf>H<inf>6</inf>, C<inf>6</inf>D<inf>6</inf>, C<inf>6</inf>H<inf>5</inf>CH<inf>3</inf>, and C<inf>6</inf>D<inf>5</inf>CD<inf>3</inf>. All deuterated species show enhanced deactivation relative to the respective nondeuterated species, with the largest effects being exhibited by the deactivation of N<inf>2</inf>O(00°1) by C6D5CD3 and C<inf>6</inf>H<inf>5</inf>CD<inf>3</inf>. The results indicate that the C-D stretch mode in the methyl group of the toluene isotopomers is the major factor responsible for the considerably enhanced deactivation of N<inf>2</inf>O(00°1), probably as a result of near-resonant intermolecular V-V energy transfer.